22 August 2006
Introduction to Proteins III Part 1
Dr. Kandace Williams, Ph.D.



3-D Structures



Tertiary Structure

  • Tertiary structure of proteins are non-symmetrical
  • Spatial arrangement of amino acid residues within a polypeptide chain that are far apart in sequence, including pattern of disulfide bonds
    • Form by thermodynamic stability and contribution of each portion to overall polypeptide chain-folding mechanisms

Myoglobin

  • One myoglobin protein contains 153 amino acids
    • MW is 16.83 kDaltons
  • ~70% composed of 8 α-helixes; remainder composed of turns and loops, forming a compact globular shape (much larger when denatured)
  • Overall shape is devoid of symmetry
  • Interior contains non-polar residues
    • except for two histidines to bind iron and oxygen
  • Exterior contains both polar and non-polar residues

Hydrophobicity and Hydrophilicity

  • Water soluble proteins are amphipathic – meaning both polar and non-polar
    • Generally fold in compact structures with non-polar cores
    • Hydrophilic –R groups (polar) --> Outside
    • Hydrophobic –R groups (non-polar) --> Inside
  • Backbone made hydrophobic by hydrogen bonding within α-helix and β-pleated sheets
  • Polar –R groups made hydrophobic by van der Waals interactions.
  • Exception: Porin within outer membrane of bacteria is hydrophobic outside (interact with lipid membrane) and hydrophilic inside (allows polar molecules through)

Protein Domains

  • Two or more compact globular protein regions connected by flexible segment of polypeptide chain
  • Protein Domains are within the same protein; do not confuse with quaternary structure which involves more than one protein

Quaternary Structure


  • Spatial arrangement of proteins containing more than one polypeptide chain
  • Each protein in a quaternary structure is called a subunit
    • Dimmers contain two identical subunits
    • Tetramer consists of four subunits

Protein Folding


  • Denature protein using:
    • β-mercaptoethanol reduces covalent disulfide bonds to sulfhydryls (-S-S- to –SH + HS-)
      • Strong reducing agent
    • Urea and guanidinum chloride can disrupt hydrogen bonds and hydrophobic interactions
  • Denaturing protein using β-mercaptoethanol, urea and guanidinum chloride destroys enzymatic activity
  • Protein activity can be recovered when β-mercaptoethanol, urea and guanidinum chloride were removed and oxygen added suggesting correct refolding of the protein with correct disulfide bonds reforming
    • if only β-mercaptoethanol removed but keep urea and guanidinum chloride, protein can reform but disulfide bonds form randomly and is enzymatically inactive
      • Randomly reformed disulfide bonds inhibit proper refolding
  • Proteins have inherent ability to form its correct tertiary structure
    • “If you leave it alone, it’ll figure out what its supposed to do”
    • Primary structure specifies conformation of the final tertiary protein
  • Protein folding in tertiary structure is not a random processes
    • Levinthal’s paradox – calculated versus actual time for a protein to fold correctly
      • Predict that it would take 1.6 x 10 e27 years to fold correctly by random search
      • Actually, E. coli produces 100 active proteins in 5 seconds
  • Cooperative transition in protein folding – “all or none”
    • Partially denatured solution has 50% folded and 50% unfolded proteins
    • Sharp transition between folding native protein and denatured unfolding protein (and vice versa)
    • Because unfolding proteins form aggregates and takes up space, it is important for proteins to have an “all or none” approach to protein folding to avoid forming aggregates
    • Chaperones help proteins to correctly fold and avoid aggregates
  • Cumulative selection aids protein folding
    • Retention of partially correct intermediates by differences in free energy and leads to increasing stability as the entire correct conformation is achieved
    • That is, as soon as the first fold is correct, it helps the next fold being correct

Prediction of 3-D protein structures


  • ab initio predictions
    • Predict secondary and tertiary structures based by amino acid sequence without reference to known protein structures
    • Computers used to determine differences in free energy of protein structures
    • Utility limited by sheer number of possible configurations
  • Knowledge-based methods
    • Amino acid sequence of unknown protein compared for sequence compatibility with proteins of known conformation by computer analysis
    • If significant match is found, it is used as an initial model
  • Predictions of secondary structures with 6 or fewer residues are 60-70% accurate
    • Conformational preferences of amino acids are not absolute
    • Tertiary interactions and microenvironment also play roles not fully understood

Human Disease

  • Several neurogenerative diseases are disease of protein misfolding.
  • Prions – self-propagating
    • Infectious protein replicates by transferring protein misfolding in the absence of nucleic acid from α-helices to form insoluble aggregates of β-pleated sheets
  • Prions are responsible for transmissible spongiform encephalopathies (TSE)
    • Fatal neurodegenerative disorders affecting humans and other mammals
    • Human = Creutzfeldt-Jakob disease (CJD) diagnosed in ~1/million/year
    • Bovine = Bovine spongiform encephalopathy (BSE)
    • Human CJD is 85% sporadic, 10-15% is inherited (fCJD), and <5% are infectious (iCJD)
      • Iatrogenic (physician-caused) iCJD transmitted by medical or surgical, human material injected, etc.
      • Variant vCJD – Can BSE be transferred to CJD

Objectives